EP0250043A1 - Dispositif d'électrolyse de vapeur d'eau à haute température - Google Patents

Dispositif d'électrolyse de vapeur d'eau à haute température Download PDF

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Publication number
EP0250043A1
EP0250043A1 EP87201125A EP87201125A EP0250043A1 EP 0250043 A1 EP0250043 A1 EP 0250043A1 EP 87201125 A EP87201125 A EP 87201125A EP 87201125 A EP87201125 A EP 87201125A EP 0250043 A1 EP0250043 A1 EP 0250043A1
Authority
EP
European Patent Office
Prior art keywords
diffusion
plate
elements
electrode
plates
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP87201125A
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German (de)
English (en)
Other versions
EP0250043B1 (fr
Inventor
Manfred Dipl.-Ing. Höcke
Rolf Dr.-Ing. Streicher
Karl Hein Dipl.-Ing. Quandt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GEA Group AG
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Metallgesellschaft AG
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Publication date
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Publication of EP0250043A1 publication Critical patent/EP0250043A1/fr
Application granted granted Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the invention relates to a device for the electrolysis of water vapor at a temperature of at least 600 ° C. by diffusion of oxygen through diffusion layers made of zirconium dioxide, each diffusion layer being provided with a metal-porous coated cathode and anode side.
  • Such a device is known from the German patent specification 3l 0l 2l0, the diffusion of the oxygen taking place through tubular diffusion layers.
  • numerous diffusion tubes are connected in parallel in order to achieve a powerful unit for generating hydrogen by electrolysis of water vapor.
  • the invention has for its object to construct the electrolysis device from flat, plate-shaped elements. This simplifies and reduces the cost of their manufacture and enables a space-saving interconnection of a large number of electrolytic cells to form a powerful unit. According to the invention, this is achieved in the device mentioned at the outset by the fact that numerous zirconium dioxide diffusion elements are used in a metallically conductive separating plate, that an electrode plate is arranged on the diffusing elements and below the separating plate, and gas flow channels are present above and below each electrode plate.
  • the water vapor can get to the cathode side of the ZrO2 diffusion element and the oxygen diffuse through the element under the action of the applied DC voltage of about 1.3 volts.
  • the oxygen flows separately from a mixture of water vapor and hydrogen to a collecting channel or into the atmosphere.
  • the mixture of H2O and H2 is drawn off via another collecting channel and the valuable hydrogen is obtained by condensing the water.
  • a residence space for water vapor is advantageously formed between the cathode side of the ZrO2 diffusion element and the electrode plate. This is not difficult in terms of production technology, since this can easily be achieved by shaping the element.
  • Fig.l are electrode plates (l) and (2), a partition plate (3), a ZrO2 diffusion element (4) and another, only partially shown Diffusion element (5) reproduced.
  • Fig.l is enlarged compared to Figures 2 and 3.
  • the diffusion element (4) is shown lifted off from the electrode plate (1) as well as from the separating plate (3) in FIG.
  • the plate (1), the element (4) and the separating plate (3) sit firmly on one another, the transition between the element and the separating plate (3) being made gas-tight. This is done, for example, by smoothing (grinding, polishing) the touching surfaces.
  • the cathode side (4a) and the anode side (4b) of the diffusion element (4) are coated with a porous metal so that the two sides are electrically conductive and at the same time also gas-permeable.
  • Numerous diffusion elements (4) belong to each partition plate.
  • the elements (4, 5) are round disks with an H shape in cross section, the middle region being thinner than the edge region.
  • the steam to be broken down electrolytically which has temperatures in the range from 600 to 1200 ° C. and preferably 800 to 110 ° C., comes from the intermediate space (6) between the separating plate (3) and the electrode plate (2) and passes through a channel 7) in a dwell (8).
  • the channel (7) is a recess in a support ring (9), cf. also Fig.3, which surrounds the recess (l0) in which the diffusion element (4) sits.
  • oxygen which is extracted from the H2O molecule passes through the element (4) through and initially collects in the collecting room (l2), cf. also Fig. 2.
  • the oxygen flows through at least one channel (l3) into the free space between the electrode plate (l) and the separating plate (3), from where it is drawn off via a collecting line. Since the elements (4) sit gas-tight in the recess (l0), the separated oxygen can no longer come into contact with the H2O-H2 mixture.
  • the H2O-H2 mixture passes from the dwell (8) through a channel (l5), see. also Fig.3, in the space (6a) and can flow from there further elements (4), which sit in the partition plate (3). Finally, the H2-rich mixture is discharged through a manifold.
  • FIG 2 it can be seen how numerous diffusion elements (4) sit island-like in the partition plate (3).
  • the zirconium dioxide of the elements is an electrical insulator, so that a DC electrical voltage of approximately 1.3 volts can be maintained between the cathode and anode sides.
  • the remaining parts of the cell namely the electrode plates (1, 2) and the separating plate (3) consist of a high-temperature metal alloy, for example a nickel alloy, and are electrically conductive.
  • the thickness of the electrode plates and the separating plates is approximately 0.5 to 2 mm
  • the height of a diffusion element (4) is approximately 0.5 to 2 mm
  • the thin central region having a thickness of approximately 0.2 to 0.4 mm .
  • the diameter of the element (4) can be approximately in the range from 20 to 400 mm, the producibility and the mechanical strength being considered.
  • the height of the space (6) through which the H2O-H2 mixture flows from element to element is approximately 0.5 to 2 mm.
  • a space-saving cell package can be generated, which is shown schematically in FIG. Insulations are omitted in Fig. 4 for simplification.
  • 4 consists of the electrode plates (1), the separating plates (3) with diffusion elements (4) embedded therein, the water vapor supply line (20) which supplies the water vapor to a distribution chamber (2l), from where it enters the Gaps (6) arrives.
  • An H2-H2O mixture leaves the arrangement through the manifold (22) and the oxygen from the respective manifolds (l2) starting to a discharge chamber (23) and into the discharge line (24).
  • This space-saving parallel connection of a large number of electrolytic cells makes it possible to generate hydrogen in any quantity.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
EP87201125A 1986-06-18 1987-06-13 Dispositif d'électrolyse de vapeur d'eau à haute température Expired - Lifetime EP0250043B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863620313 DE3620313A1 (de) 1986-06-18 1986-06-18 Vorrichtung zur hochtemperatur-elektrolyse von wasserdampf
DE3620313 1986-06-18

Publications (2)

Publication Number Publication Date
EP0250043A1 true EP0250043A1 (fr) 1987-12-23
EP0250043B1 EP0250043B1 (fr) 1990-10-31

Family

ID=6303158

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87201125A Expired - Lifetime EP0250043B1 (fr) 1986-06-18 1987-06-13 Dispositif d'électrolyse de vapeur d'eau à haute température

Country Status (3)

Country Link
EP (1) EP0250043B1 (fr)
DE (2) DE3620313A1 (fr)
ES (1) ES2018245B3 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011110677A1 (fr) * 2010-03-12 2011-09-15 Commissariat à l'énergie atomique et aux énergies alternatives Architecture d'electrolyseur a haute temperature, a production cible elevee par cellule d'electrolyse et taux de degradation des cellules limite

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4123694A1 (de) * 1991-07-17 1993-01-21 Merck Patent Gmbh Verbundsystem
DE19540993C1 (de) * 1995-11-03 1997-07-24 Richard Krauss Verfahren zur Einsparung fossiler Kraftstoffe und der bei ihrer Verbrennung entstandenen Schadstoffe durch Zumischung von Wasserstoff und Sauerstoff, die in einem Dampfelektrolyseur unter Druck aus alkoholhaltigem Wasser unter Verwendung der Abgaswärme von Verbrennungsmotoren erzeugt werden sowie Vorrichtung zur Durchführung des Verfahrens

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3101210A1 (de) * 1981-01-16 1982-07-29 Dornier System Gmbh, 7990 Friedrichshafen "gestaltung einer moduleinheit nach dem hochtemperatur-dampf-elektrolyse-verfahren"
DE3325285A1 (de) * 1983-07-13 1985-01-24 Robert Bosch Gmbh, 7000 Stuttgart Festelektrolytrohr fuer die hochtemperatur-wasserelektrolyse
EP0158760A1 (fr) * 1984-03-29 1985-10-23 VISCOBELL S.p.A. Montage-bloc de cellules d'électrolyse du type filtre-pressepour l'èlectrolyse de l eau

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3101210A1 (de) * 1981-01-16 1982-07-29 Dornier System Gmbh, 7990 Friedrichshafen "gestaltung einer moduleinheit nach dem hochtemperatur-dampf-elektrolyse-verfahren"
DE3325285A1 (de) * 1983-07-13 1985-01-24 Robert Bosch Gmbh, 7000 Stuttgart Festelektrolytrohr fuer die hochtemperatur-wasserelektrolyse
EP0158760A1 (fr) * 1984-03-29 1985-10-23 VISCOBELL S.p.A. Montage-bloc de cellules d'électrolyse du type filtre-pressepour l'èlectrolyse de l eau

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Band 100, Nr. 24, 11. Juni 1984, Columbus, Ohio, USA DIETRICH, G.; SCHAEFER, W.; DOENITZ, W. "Development of thin film cells for high temperature electrolysis" Seite 501, Spalte 1, Zusammenfassung-Nr. 199 810a *
CHEMICAL ABSTRACTS, Band 101, Nr. 24, 10. Dezember 1984, Columbus, Ohio, USA DIETRICH, G.; SCHAEFER, W. "Advances in the development of thin-film cells for high temperature electrolysis" Seite 461, Spalte 1, Zusammenfassung-Nr. 218 547j *
CHEMICAL ABSTRACTS, Band 101, Nr. 24, 10. Dezember 1984, Columbus, Ohio, USA DOENITZ, WOLFGANG; ERDLE, ERICH; HERMEKING, HAJO; KOCH, ALFRED; KOCK, WULF; ROETTENBACHER, REINHARD; SCHAEFER, WOLFGANG; SCHAMM, REINHOLD; SCHMIDBERGER,RAINER "High temperature electrolysis of water vapor: Hot Elly, phase 2A" Seite 461, Spalte 1, Zusammenfassung-Nr. 218 545g *
CHEMICAL ABSTRACTS, Band 102, Nr. 6, 11. Februar 1985, Columbus, Ohio, USA VIGUIE, J.C. "Fabrication and characterization of a set of electrolytic cells for the electochemical reduction of water vapor at 850oC" Seite 468, Spalte 2, Zusammenfassung-Nr. 53 042w *
CHEMICAL ABSTRACTS, Band 104, Nr. 16, 21. April 1986, Columbus, Ohio, USA GUTH, ULRICH; MOEBIUS, HANS HEINRICH "Hydrogen production by high temperature electrolysis of water vapor in solid electrolyte cells" Seite 145, Spalte 1, Zusammenfassung-Nr. 132 353t *
CHEMICAL ABSTRACTS, Band 95, Nr. 8, 24. August 1981, Columbus, Ohio, USA ACCORSI, ROLAND "Hydrogen production by high-temperature electrolysis of water vapor in stabilizedzirconia solid electrolyte cells" Seite 533, Spalte 1, Zusammenfassung-Nr. 69 850f *
CHEMICAL ABSTRACTS, Band 95, Nr. 8, 24. August 1981, Columbus, Ohio, USA VIGUIE, J.C.; BERNHARD, H. "Electrolysis of water vapor at 850oC. Characteristics of a 50-cm2 flat cell" Seite 533, Spalte 2, Zusammenfassung-Nr. 69 852h *
CHEMICAL ABSTRACTS, Band 95, Nr. 8. 24 August 1981, Columbus, Ohio, USA ACCORSI, R. "Electrolysis of water vapor at high temperature in a cell with stabilized zirconia solid electrolyte" Seite 533, Spalte 2, Zusammenfassung-Nr. 69 853j *
CHEMICAL ABSTRACTS, Band 99, Nr. 12,19. September 1983, Columbus, Ohio, USA VIGUIE, J.C. "Construction and characterization of an electrolyzer for electrochemical reduction of steam at 850oC" Seite 490, Spalte 2, Zusammenfassung-Nr. 95 780k *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011110677A1 (fr) * 2010-03-12 2011-09-15 Commissariat à l'énergie atomique et aux énergies alternatives Architecture d'electrolyseur a haute temperature, a production cible elevee par cellule d'electrolyse et taux de degradation des cellules limite
FR2957363A1 (fr) * 2010-03-12 2011-09-16 Commissariat Energie Atomique Architecture d'electrolyseur a haute temperature, a production cible elevee par cellule d'electrolyse et taux de degradation des cellules limite
US9238871B2 (en) 2010-03-12 2016-01-19 Commissariat A L'energie Atomique Et Aux Energies Alternatives Architecture of high temperature electrolyser, with high target production per electrolysis cell and limited cell degradation rate

Also Published As

Publication number Publication date
EP0250043B1 (fr) 1990-10-31
DE3765854D1 (de) 1990-12-06
DE3620313A1 (de) 1987-12-23
ES2018245B3 (es) 1991-04-01

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